I make shortcuts for my most-used programs and directories in my Start Menu, and then (if needed) I preface them with a unique letter or number. This allows me to press the Windows key once, then one key to open a program.
The key is that the starting letter does NOT have to be part of the actual program or location name. For example, I used to use Internet Explorer as my main browser, so I got used to using the "windows, i" to open it up. I started using Firefox, but was still used to the key combination (I'm a kinetic memorist), so now Firefox is named "iFirefox" in the Start Menu.